Direct azo dyes containing 3,5 dihydroxy benzoylamino groups



Patented Feb. 25, 1947 UNITED "STATES, PATENT orncsz DIRECT AZO; DYES CONTAINING 3,5 DIHY- DROXY BENZOYLALIINO GROUPS Swanie S. Rossander and Chiles E. Sparks, Wilmington, Del., and James W. Libby, Jr., Louisville,;Ky., assignors to E. L du Pont de Nemours 8;. Company Wilmington, Del., a corporation oi.

Delaware Nonrawmg. Ap lication July 6,1944,

Serial No. 5313.730,

wherein R represents an aromatic radical containing at least one azo group. For example R may comprise a monoazo group such as or other configurations of the azo group. One or more 3,5-dihydroxy-benzoylaminogroups may be present in the radical R. They are carried directly by the aryl nuclei of the components. When more than one such group ispresent, they may be present in the same .or in different components of the dye. The dyes carry water solubilizing groups sufiicient to make them soluble in water, such as sulfonic acid. or carboxy. The dyes find use as direct dyes, more particularly for dyeing cellulosic fibers, such as cotton and regenerated cellulose rayon. Dyeings made with these dyes are susceptible to after-treatment with formaldehyde which improves the fastness properties of'the dyeings.

A type of direct, azo dyes of somewhat similar structure is known, except that the end roup is an azo-resorcin group, which is made by'coupling the diazo of an amino azo dye withresorcin, such a compounds being represented in general by the, formula: r

wherein R has thev same value as in the abovedescribed formula. The latter dyes are desirable in that dyeings can be-made with them from dyebaths in a manner similar to that of making direct dyeings-v, The best, washing iastness properties are attained with, the ,azo-resorcin-end- 7 Claims. (01. 260159")'- 2 group type of direct azo dyes by after-treating the dyeings with formaldehyde, wherein little, if any, change in shade is produced. Thewash ing fastnessof such dyeings is similar to the diazov ordeveloped dyes and better than dyeings made with direct dyes and the brightness approaches that of direct dyes. Notwithstanding, however, the excellent general and special prop.- erties of the azo-resorcin-enda-group type. of direct azo dyes for cotton, it was desirable to pro.- vide azo dyes having the ease of application of those dyes and of direct dyes together with somewhat greater stability than either the azo resorcin or direct dyes, especially in respect to brightness and light fastness.

It is among the objects of the present invention to providenew soluble azo dyes which are capable of dyeing cellulosic fibers, such as cotton and regenerated cellulose rayon by direct dyein methods, the dyeings from which are capable of being improved by after-treatment with formaldehyde,

and which also have unusual brightness and light 4 fastness properties as compared to dyes which are similar except that the end group or groups are azo-resorcin. Another object of the invention is to provide methods for manufacturing the new dyes. Other objects of the invention will be apparent fromthe following description.

The objects of the invention are attainable in general by providing an amino azo compound having at least one aryl nucleus. substituted by a primary amino group and then. forming with each primary amino group, as by condensation with a halide of 3,5- di(carbomethoxyeoxy).-ben- I zoic acid or a halide of diacetyl-3,5-dihydroxybenzoic acid, a dihydroxybenzoyla'mino group. The objects are attained when any aryl nucleus of any component of the. azo dye is directly substitutcd by the meta-dihydroxy-benzoylamino group. A. component of the azo radical R of th general formula may comprise more than one aryl nucleus and accordingly the component may contain more than one meta-dihydroxybenzoylamino group. It is essentia1 that the azo radical R contain a solubilizing group or'groups sufficient. to make the products soluble in water, such as sulfonic acid and carboxy.

It has now been. discovered that dyeings produced with azo. dyes thus substituted by the dihydroxy benzoylamino vgroup artv amenable to v 2416,54? W 3 r r 4 after-treatment with formaldehyde and that 30 minutes or until thecondensationls completed. such treatment greatly improves the washing Then sufiicient sodium carbonate is added to profastness of the dyeings. It has further been disduce a definite alkaline reaction to Brilliant Yelcovered that the 3,5-dihydroxy-benzoylamino low paper for hydrolyzing the carbomethoxy-oxy group when thus substituted on the azo comgroups to hydroxy. Finally 150 parts of sodium pound does not in itself impair the light fastness chloride are added to salt out the product and the of the nuclear dye molecule as does the substituproduct is separated by filtration. The dye is tion of an azo-resorcinol end component to such thendried at 70: C. g a dye nucleus. *Thetobjects of then-invention may, 1 Theproduct -1s,represented.1 n ts acid form by therefore,be attained by using as the starting the formula compound any amino-substituted azo dye such 'This' product when dyed on viscose rayon by as R(NH2)11. which also contains a Water solu- 2 direct dyeing methods is blue-red. When afterbilizing group or groups suflicient to render the treated With aqueous alkaline formaldehyde soproducts soluble in Water and m(m'rporujir-1-g,i lution; the dyeing has excellent washing fastness dihydroxy-benzoyl group therein, as by condend y good h t ast e s. T e dy 60msation. By the above described condensation, pa esf a brightness With the direcii there results a compoulid which produces direct mg made with the direct dye represented in its dyeings having-considerable improvement in the acld rm by the formula general stability of the dyeing. After treating 7, SOSH withformaldehyde, the washing fastness of the dyeing are excellent and the dyes approach the Eggs-0N developed azo dyes inthis respect. The bright- 39 v ,H i

nessa d l t ss Properties after formaland the light fastness and washing fastness are yd t a t' r osely appr a h that f far superior. The fastness to light is somewhat the' direct azo dyes having the basic azo strucbetter than a similar dyeing similarly made with time which is represented by the: symbol R in the dye which in the form of its acid is repretheabove formula'or by R-.-NH2, than the type 735 sented by the formula,

V CE e i Hess NHOO N= 00H where the last component is the'azo-resorcin Emmett: 2 m 9 as th p "1 Dissolve 1'7 parts of the dye Z-naphthylamine- V R I f ,T 6,8-disulfonic'acidm-toluidine (condense the V primary amino 'gr'oup'with p-nitro-benzoyl-chlof O B g [ride and-thereafter reduce the nitro group to i r I v a amino) m-amino-phenyl-methyl-pyrazolone in flhei t on Will be more fully Set Q in approximately 2,000 parts of water. Cool to 0-5 thejfollowineimore t i d s r pt which ,7 p '0, and; while maintaining faint'alkalinity to Brild s est e given-as. representative 'liant Yellow paperand excellent agitation at said an 1u rati e bq m Q ei l d temperature, gradually add over a period of 70 as l a s oo s a expressed minutes a solution composed of 9 parts of 3,5-din p r y e unless he i e l o '1 (carbomethoxy-oxy) -benzoyl chloride and 300 'Afi I parts of acetone. 190 parts of /2 normal sodium r H carbonate-solution'are added during thecourse Dissolve 34. pa ts'oft d a ody m F of this addition-to maintain slight alkalinity. benzene psulfonic acid+2- (4-amino,-benzoyl- After all the acidchloride has been addedfstir.

'amino) -5-naph thol -'7-sulfonic acidin 1250 pans at 0-5 C. for an additional 90 minutes and then "'ofyv'va r at 0; S y add o s solut 7 stir for about'8 hours to allow the condensation u in a period of-70 minutes a solution of -18.8 "to complete. Make the solution definitely alka- 1 parts of 3,5.-di-(carbomethoxy-cxy) -benzoyl ch10; line to Brilliant Yellow test papers by the addi-- fride in 250 parts of acetone" whilst stirring and tion of soda ash and heat to 70" C; 1 Then gradufmain-taining the'te'mperatu-re at 55 C. During 'allysalt out by addin g 200 parts ofsodium chlocondensation th'emixture of reactants should'also ride. Then filter ofi the precipitateddyestuif "be maintained just alkaline'to Brilliant Yellow and dry at C.

f paper by gradually adding 1'70 parts o'f 0.5nor- In its acid form the compound isrepresent'ed -malsodium carbonate'solutionas the'neutralizing by the formula .fso'an f '7 a V V in v =ff- 1 0H N=N- -NHC OON=NCH I i N T V 1-1\i H OzS r 7 Ha V ,1 V|' e, I V v 1 V I Y Q O lagentis needed. Afterftheaddition of. the acid .Afidyein'g made with, this product, on rayon chloride i'scoinpleted; the mixture is "stirred for fabric'isa red-yellow Shade which has very'goo'd aerate? washing 'fa'stness "and good light 'fastness when the dyeing has been after-"treated with an alkaline solution of formaldehyde. As compared to dyeingsmade-with the nuclear direct'dyeand' the dyeing made with a dye havingtthe azo resorci'n group on the last'component of the nuclear azo radical, the new dye is superior in the I-respects noted the preceding example.

EXAMPLE '3 Dissolve 8 parts of the dye represented by the 1 formula (ZenaphthyIamine-GB-disulfonic acidm-toluidinem-toluidine+urea-m-phenylene diamine Hos I 'm 1200 parts of water. Heat'thissolutionto 55 "Gland while maintaining good agitation, add over the course of 90'minutes a'solution of '7 .2 partsof 335-.di(carbomethoxy-oxy) benzoyl chloride in 225ipartsof acetone. Duringthis addition, main- 'soda'a-sh, hydrolyze the carbomethoxy oxy groups tohydroxy andg final-ly preciplitajte' the dye'by the addition of salt. rilter ofifthe product and 1 dyeing on 'rayon piece "goods is yellow-brown I in shade, and has very 'goodwas'lring fastness and :goodlig'ht fastness when after-treated with an alkaline solution -'of formaldehyde. As compared to the corresponding direct amino 'azo dye "and the dyes having 'azo .re'sorcin and components,

the improvement in properties is similar to {that described in'thepreceding-examples.

In the iform or its acid "the product represented'byitheformula I v The, following exa-mp'les, .in Tablel werepre-v pared :by methods similar iaoQthose described in the foregoing examples. -In LtheJtalo'le the arrows are directed away from the diazo component and the components are set down in the order of coutain a slightly "alkaline test 'on Brilliant Yellow p n d -t t -fi a du ts, a h

test papers by the addition of "80 parts 'of' nor- "mal sodium carbonate solution as required. At thispo'int test the completeness 'of the condensationgby taking a small sample from the reaction mixturepdyeing'it on cotton and developing 40 of the dyeing with beta-naphthol. The development with 'betanaphthol "is done bytreating /2 of the dyeing first with an aqueous solution-of nitrous acid to diazotize the compound on the fiber and then treating with an alkaline solution of beta-na-phthol. The presence of free amino groups is indicated if the developed piece is-of a deeper shade than'the direct dyeing, In case the *c'ondensationis not complete, add slowly a'second portion of 2 parts of 3,5-'di--(carbomethoxy-oxy) benzoyl chloride dissolved in parts of acetone "to the reaction mixture in the same manner as described above. A second test should indicate complete condensation;

primary amino group :of 'the samino 'zazo scornpounds thus represented was condensed with 3,5- di-(carbomethoxy oxy) -:benzoyl chloride. in aqueous, slightly alkaline solutioniand' the :carbomethoxy-oxy groups were'lhydrolyzedito; hydroxy,

thereby producing the corresponding derivatives having the typical formula V 1 v in Nil-006i I aldehyde after-treated dyeing on regenerated cl- "lulos'e rayon. These fdyes have the desirabl'e i-mproved properties of "the dyes of the foregoing examples: i

Table 1 E The.3,5-dihydroxy-benzoyl derivatives of thefollowing amino azo dyes Shade ,p-Amino-benzoyl-p-phenylene-diamine 3 (Z-amino-5-naphtho1 7*sulionic acid)? 1 med. pAmino-benzoyl-p-toluylene-d anline' {2-(3-amino-benzoyl-amino)-5-naphthol-7esu1ionic acidh Do.

p-Amino-benzoyl'm-phenylcne-dlamme .3 .[1-(3Gammo-phenyl)-5-pyrazolone-3-carboxylic acid]; Yellow.

.2'Naphthylarnine-6,8 disulionic acid m toluidine -3 ln-toluidine condense the .primary amino Orange.

group with p-nitro-benzoic'acld chlorideand thcreafter reduce nltro group). r -"oxalyl-pephenylcne-diamine l-naphthylamme-6-sulionic.acid -v l-na'phthylamine-G-sulfonic acid Blue. I

2-naphthol-7-snlfonic acid (rt-hydrolyze the 'ox'alyljgroup to amino). v 2-Naphthylamine-6,8-disulionic acid 'm-toluidine --moluidine condense the primary amino group 1 with p-nitro-bcnzoic acid chlorideand-thereaftcr reduce the nitro group) --v m,m-diamino-dipheny1-urea.

2-Naphthylamine-(S,8-disulf0nic acid m-toluidlne m-toluldine condense the primary amino group Do.

with p-nitro-benzoic'acid chlorideand vthereafterreduce the'nitrogrou ln-phenylene diamine.

Orange.

(m-Amino-iormanilide); 3 6,5-dihydroxy-7,7-disu.lfo-2;2-dinapht yl' urea H-hydrolyze'theformylgroup s to "Scarlet.

amino). Amino-azo toluene sulfonic acid 3 ,5-di(4-arnino-benzoyl)-amino-benzoyl-2-amino-5-naphthol-7-su1fonic acid; Brown. 2-lgja ilhthylamlne-6-sulfonic acid l-naphthylamlne-(i-sulfonic acid -mm-to1uidine -r m .m'-diamino- Do.. p eny urea.

(oxalyl-p-phenylene-diamine l-nnphthylamine-G-sulfonic.acid l-naphthylamine 6 sulfonicacid and Blue. hydrolyze oxalyl gro'upsto amino) 3 -[2-'(p=amluo-benzoylammot 5-naphthol 7-sulfonic.acidh; I

Oxalyl-p-phenylcne-diamine l-naphthylalnine-B-sulfonic acid l-naphthylamme-li-slilfonic acid Do.

2-amino-5-naphthol-7-sulfonic acid hydrolyze oxalyl group to amino); y i

Then make the dye-solution definitely alkaline to Brilliant Yellow test papers by the addition of I Any of the described condensation products of amino-azo dyes can be made by identical proc-.

esses except that :a halide of diacetyl-3,5-dihydroxy-benzoic acid is used instead of 3,Y-di(car ybomethoxy-oxy) benzoyl chloride. Y Similarly other halides of 3,5-di-(carbomethoxyl-benzoic The acid can be used such. as the bromides. methods of condensing with the amino-azo compound in aqueous solution arein general the same in'both cases. The following is a typical example:

. EXAMPLE 16 "Heat to as -60 c. five parts of" the dye, aminoazo. benzene sodium 'sulfonate 2- (4'- aminobenzoylamino) -5-naphthol-7-sulfonic acid which is dissolved in 300 parts of water. Add a chloroform solution of 4 parts of diacetyl-3,5-dihydroxy-benzoyl chloride 'to' this solution slowly.

During the period of this addition, maintain good agitation, ,a temperature of 55-60 C., and a slight alkalinity to Brilliant Yellow papers, by the addition of'small amounts of soda ash. After the condensation is completed, add sodium hydroxide until the solution is definitely alkaline 'to Brilliant YellQW test papers and raise the temperature to 80 C. to complete the hydrolyzation.

Finally salt out by adding 60 parts of salt. Filter .011 the dye and dry it. The, product is a water soluble dye which dyes cellulosic fibers from dyebaths. A dyeing on cottoncloth is of a blue-red shade and wh'e'hafter-treated with an alkaline "formaldehyde' solution exhibits very good washfling fastness' Theproduct' is represented by the same formula as the product of Example 1.

I ExA urLE 17 Dissolve -2 parts of. the dye, amino-azo-benzene-p-sodium. su1fonate J-acid, in water and add 1 parts of diacetyl-3,5-dihydroxy-benzoyl chloride in chloroform solution slowly while main- "taining. good agitation and a slight alkalinity to Brilliant Yellow test paper. Raise the tempera-. 1 ture graduallyto 609C. and then add 1 part more of the acid chloride dissolved in a small amount of chloroform. Stir the mixture for 3 hours at 60 C. to complete the condensation. During this period maintain slight alkalinity to Brilliant Yel- 1 low papers by the addition of small amounts of soda ash. Finally, make the dye solution definitelyalkaline'to Brilliant Yellow papers by the addition of soda ash; raise the temperature of ,the solution; to;.80- C.,and holdiit there for. 1 .hour to complete the. hydrolyzation of the acetyl,

equivalent to of the yolume of the dye solution and 4 parts of a 2 normal solution of sodium hydroxide; stir for several minutes. Finally, add i 4 parts of a 2 normal solution of acetic acid. The. dye slowly precipitates out upon further stirring, I

andis filtered off and dried. The product is a water soluble dye which dyes cellulosefibers from $alt out by adding anamount of salt dyebaths and is represented by the ,formula V on A. die g 6h. .v "re-we: oth u red. i.

intermediate with the diazo o f an amino V which may be a single compound or an aznino shade, and when after-treated with aqueous alkaline formaldehyde possesses very good ash; .ing fastness. H v

met od ofrmd 'c s pro uct An alternative. inaccordance with this invention consists in con,-

densing the intermediate containing the amino group with either diacetyl-3, 5-dihydroxy.-ben:- zoyl chloride or with 3,5-die(carbomethoxy-oxy);- benzoyl chloride and then coupling the resulting base substituted azo compound, and finally subjecting the protective acetyl or carbomethoxy. groups to an alkaline hydrolysis as hereinbefore described for forming the'dihydroxy benzoyl amino group or groups. The following example is'illustrative.

EXAMPLE 18 Diss'olve 3 parts of J-aoid (2,5,7-amino-naplithol-sulfonic acid) in about 200 parts'of water with the aid of enough soda ash to leave the solution just alkaline to litmus paper. Add sulficient acetic acid to bring the solution just acid to litmus. Then add 2 parts of a 2 normal solution or sodium acetate. Dissolve 3 parts of 3,5-

di-(carbomethoxy-oxy) -benzoyl chloride in a small amount of acetone. While continually stirring the J -acid solution at roomtemperature, add slowly the acetone solution of the acid chloride. At the same time, add a solution of sodiur'n'carbonate slowly to maintain the pH of the J-ac'id solution just .onthe alkaline side to Brilliant Yellow test papers. After stirring for one hour, there should be no test for free amine as determined by removing a small sample, acidifying .with hydrochloride acid; adding a few; drops Iof sodium nitrite solution and spotting this solution on filter paper impregnated with phenyl J a cid. and alkali. X T

. Slurry 1.1. parts :of 'p-amino-benz'oyl-p-phenyl- .enediamine in parts of water. Add 1 part of hydrochloric acid, stir to completesolution and add ice to bring the temperature .to 5 0. Add

0.7 part sodium nitrite and stir one-half hour, maintaining a light excess of nitrite as indicated by starch-potassium iodide test paper throug' h the'addition of additional nitrite if necessary. Hold the temperature between 6. and; 8? .Q. ..At

theend of theone-half hour period, destroy the ":excess nitrite by the addition of sulfamic acid.

represented by the formula 1 Cool the solution of N-(3,5-dicarbomethoxyeoxybenzoyl) -2,5,7-amino-naphthol-sulionic acid prepared above, and add two parts of sodium carbonate. To this solution add slowly the solution of tetra'zo p-amino-benzoyl-p-phenylene-diamine prepared aboveand stir overnight. To thisdye solution then add? parts of "aqueous ammonia.

Stir for 3 hoursat room temperaturei,' then add 24 parts of acetic acidand hydrolyze offlthe carbomethoxy groups by heating. to C. The solution at'this point-isfiltered ofi 'anddried. This product is identical with the first dyestufi set forth in Example 4 and'in its acid form it is 'and'adding ojlfi gram of sodiumca-rbonate: to as sist the; dyeing diluting withwater at 160 F. to a total volumeof 1100 cc. while. stirring and then adding 50 cc. or a solution of Glaubers salt. Wet outa 10 gram piece: of' viscose rayon: with water,; squeeze. partially dry andplace-in the dyebath. Raise the temperature of the dyebath to 180190 F. during a period of minutes and hold at that temperature for 1 hour. Stir at frequent intervals during the dyeing. At the end of 1 hour remove the dyeing and rinse with cold water.

The after-treatment with formaldehyde in a fresh bath is done by adding the rinsed dyeing m: y 1 direct; cotton. azo. dye represen d y; the.

V i 3. .0133... R-NH-oO O i wherein Rrepresents an aromaticradical: conx-L taining atleast one aryl-nucleusaandrat least. one azo group; andiwherein-Jat least one m ,m.'-dihy-' droxy-benzoyl amino group is substituted directly 0112,11 aryl: nucleus; saidcompound containing water solubilizing groups suflicient to render the dye soluble in water. q 2. A direct cotton azo dye in accordance with claim 1 in which an aryl nucleus of only one component is substituted by at least one m,m'-dihydroxy-benzoyl-amino group.

3. The azo dye which in the form of its acid is represented by the formula i g on HOaS- NH-COONH-O 0C? H 4. The azo dye which in the form of its acid is represented by the formula I I OH 6 NHCO Hols om l from the above operation to 500 cc. of water at a temperature of 130-140.F. and then adding SOaH to the water 10 cc. of a 10% formaldehyde solution cc. of approximately 37% formaldehyde by weight, diluted to 250 cc. with water), plus 0.3 gram of sodium carbonate. Hold the aftertreating bath at this temperature for 20 minutes, remove the dyeing, rinse and dry.

The after-treatment in the dyebath may also be done by an alternative procedure which is the preferred procedure because of its economy and ease of application. Accordingly, at the end of the dyeing 'period, add to the dyebath 10 cc. of the 10% formaldehyde solution at the bath temperature and 0.3 gram sodium carbonate or sufficient to mak the solution alkaline. Turn the dyeing for 20 minutes, then remove, rinse and dry.

From the foregoing disclosure it will be recognized that the invention issus'ceptible of modification Without departing from the spiritand scope thereof and it is to be understood that the invention is not restricted to the specific illus-e trations herein set forth.

We claim:

containing a 3,5-dihydroxy-benzoylamino group 1 which comprises making a water solution of a soluble azo dye having two primary amino groups 5. The azo dye which in the form of its acid is represented by the formula NH-C O pH value just alkaline to Brilliant Yellow paper until the primary amino group is condensed with said halide, then making the reaction mixture definitely alkaline to Brilliant Yellow paper and heating the mixture until the condensed substituent is hydrolyzed to a 3,5-dihydroxy-benzoylamino group.

7. The process of making an azo compound directly attached to aryl nuclei thereof, heating the solution in the presence of a compound of we grbnp'driisting' bf di-(c' rbemethox -emf REEERENCESCIIED? benzoyl chloride and d1-acety1-3,5-d1hydro y- The:f ]1 wj er n s a b b d h h benzoyl chloride whilst maintaining a condensaof this patent: tion temperature anda pH value just alkaline to r l 7 7 r i v Brilliant Yellow paper until the primary amino 5 UNITED STATES PATENTS groups are condensed with said halide, then mak- N m e 1 D ingthe reaction mixture definitely alkaline to 13433727 'pleischhauer Jan' 19 7 Brilliant Yellow paper and heating the mixture 2,132,347 Murphy et a1. Dec. 5, 1939'. until the condensed 'substituents are hydroylzed 2,357,977 Rossander Sept. 1-2;1944 to 3, ihydroxy-ben y1-amino roups. I --2,1 95;0s9 Kollmann Mar. 2e,--194o SWANIE SLROSSANDER. w FOREIGN PATENTS CHILES E; SPARKS. Number V 7 Country Date JAMES W. LIBBY, JR. 370,606 British Apr. 14,1932

Certificate of Correction Y Patent No. 2,416,547. February 25, 1947 SWANIE S. ROSSANDER ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 3, line 56, for diazo read disazo; column 6, line 9, for and components read and components; lines 26 to 29, for that portion of the formula reading -NHCOO read -NHOOQ a column 7, line 58, for cellulose read cellulos'ic; column 8, at the bottom of the page, left-hand portion of the formula, for

on on" on @0011: read @0011:

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 22nd day of April, A. D. 1947.

LESLIE FRAZER,

First Assistant of Points. 

